Aliphatic amines are commonly employed for the synthesis of products or intermediates which are used in the pharmaceutical or agrochemical industries. Amines of this type are also used as precursors for the production of polymer such as polyurethanes.
The hydroaminomethylation reaction was reported by Reppe (Liebigs Ann. Chem. 1953, 582, 133-161), using a cobalt catalyst. This reaction comprises a one-pot tandem hydroformylation/amination reaction of an olefin, in which the aldehyde from the hydroformylation of the olefin reacts with a primary or secondary amine to form a secondary or tertiary amine, respectively.
U.S. Pat. No. 3,513,200 describes the hydroaminomethylation of an olefin in the presence of a rhodium/PPh3 catalyst for the synthesis of tertiary amines. Hydroaminomethylation reactions are also known from DE 10321421, U.S. Pat. No. 7,220,884 or Behr et al. (Tetrahedron Letters 51 (2010) 2438-2441). To improve the performance parameters of the reaction, the use of cocatalysts, especially based on rhodium and on iridium, allows rapid formation of amine. The rhodium intervenes in the hydroformylation reaction, the iridium in the catalytic reduction of the intermediate imine or enamine. Hydroaminomethylation reactions are also known in which polymer is obtained directly. Müller et al. showed that the use of polyfunctional substrate or polyfunctional amine allows the preparation of polyamine dendrimers by hydroaminomethylation (Müller et al., Org. Biomol. Chem., 2006, 4, 826-835).
Wang et al. showed the efficacy of hydroaminomethylation reactions on fatty olefins in the presence of various amines (Wang et al. Applied Catalysis A: General 272 (2004) 151-155). The reactions were carried out in emulsion, and required the use of surfactants such as CTAB, entailing additional steps for recovery of the substrate and the catalyst. Behr et al. used the methyl esters of oleic acid in hydroaminomethylation reactions in which the amine used is, for example, proline (Eur. J. Lipid Sci. Technol. 2014, 116, 477-485; Eur. J. Lipid Sci. Technol. 102 (2000) 467-471). This type of reaction exclusively only forms amines from monounsaturated fatty olefins. The hydroaminomethylation of oleyl alcohol is also known from Behr et al., Chemie Ingenieur Technik, 2007, 79, 5, 621-636.